CN104846439A - Polycrystalline group III metal nitride with getter and method of making - Google Patents

Polycrystalline group III metal nitride with getter and method of making Download PDF

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Publication number
CN104846439A
CN104846439A CN201510178981.3A CN201510178981A CN104846439A CN 104846439 A CN104846439 A CN 104846439A CN 201510178981 A CN201510178981 A CN 201510178981A CN 104846439 A CN104846439 A CN 104846439A
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chamber
crystal
metal
nitride
getter
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马克·P·德伊夫林
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Soraa Inc
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Soraa Inc
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
    • C30B28/06—Production of homogeneous polycrystalline material with defined structure from liquids by normal freezing or freezing under temperature gradient
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B9/00—Single-crystal growth from melt solutions using molten solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The present invention provides a polycrystalline group III metal nitride with getter and a method of making, and particularly provides a gallium nitride containing crystal. The crystal has a crystalline substrate member having a length greater than about 5 millimeters and a substantially wurtzite structure characterized to be substantially free of other crystal structures. In a preferred embodiment, the other structures are less than about 1% in volume in reference to a volume of the substantially wurtzite structure. The crystal also has an impurity concentration greater than 1015cm-3 of at least one of Li, Na, K, Rb, Cs, Ca, F, and Cl and an optical absorption coefficient of about 2 cm-1 and less at wavelengths between about 385 nanometers and about 750 nanometers.

Description

There is polycrystalline III metal nitride and the manufacture method thereof of getter
The divisional application that the application is the applying date is on December 11st, 2009, application number is 200980154756.9, denomination of invention is the application of " polycrystalline III metal nitride and the manufacture method thereof with getter " (PCT/US2009/067745, enter State Period date on July 15th, 2011).
The cross reference of related application
The right of priority of the commonly assigned temporary patent application No.61/122332 that application claims was submitted on December 12nd, 2008, it is incorporated to herein by reference for all objects.
Technical field
The present invention's generality relates to the material of process for crystal growth.More specifically, the invention provides the crystal nitride material being suitable for use as the raw material carrying out the crystal growth containing gallium nitride crystal with ammonia alkali or propylhomoserin technology, also can comprise other aspects.In other embodiments, the invention provides the method being suitable for synthesised polycrystalline nitride material, but will be appreciated that other crystal and material also can be processed.This crystal and material include but not limited to GaN, AlN, InN, InGaN, AlGaN and AlInGaN, and for the manufacture of the other materials of block or patterned substrate.These blocks or patterned substrate can be used for multiple application, comprise photoelectric device, laser apparatus, photodiode, solar cell, photoelectrochemistry hydrogen production by water decomposition and hydrogen power generation, photodetector, unicircuit and transistor and other equipment.
Background technology
The crystalline material of nitrogen gallium is used as to manufacture the substrate of conventional photo device as blue light emitting diode and laser apparatus.This photoelectric device is formed usually on the composition sapphire different from nitride layer or silicon carbide substrates.In common metal organic chemical vapor deposition (MOCVD) method, carry out the deposition of GaN in gas phase by ammonia and organometallic compound.Although success, the routine growth speed obtained is difficult to provide the course of blocks of overall GaN material.In addition, dislocation desity is also very high, causes the poor-performing of photoelectric device.
Propose to obtain element nitride crystal by ammonia thermal synthesis.The hot growing method of ammonia estimates to have easily extensible, as at Dwilinski, Deng [the J.Crystal Growth 310 of people, 3911 (2008)], Ehrentraut, Deng [the J.Crystal Growth 305 of people, 204 (2007)], [the J.Crystal Growth 300 of the people such as D ' Evelyn, 11 (2007)] and as described in [Crystal Growth & Design6,1227 (2006)] of the people such as Wang.Ammonia thermal means generally needs polycrystalline nitride raw material, and then recrystallization is on kind of crystalline substance.Continuing challenge for the GaN crystal of ammonia heat growth is the remarkable content of impurity, causes crystal coloured, such as, and yellow, green, grey or brown.Residual impurity can cause the photoabsorption of the photodiode manufactured over the substrate, negative impact efficiency, and also can make specific conductivity deterioration and/or produce stress in crystal.A source of impurity is polycrystalline nitride raw material.
Such as, the gan being carried out hydride gas phase epitaxial growth by relatively expensive vapor phase process shows extraordinary light transmission, in about 385 nanometers to the photoabsorption coefficient of about 620 nanometer wave strong points lower than 2cm -1[people such as Oshima, J.Appl.Phys.98,103509 (2005)].But, we notice the gallium nitride of the most transparent ammonia heat growth be flaxen and in about 465 nanometers to the photoabsorption coefficient of about 700 nanometer wave strong points lower than 5cm -1[people such as D ' Evelyn, J.Crystal Growth300,11 (2007) and United States Patent (USP) 7,078,731].
Propose the method for several synthesised polycrystalline nitride material.The people such as Callahan [MRSInternet J.Nitride Semicond.Res.4,10 (1999); United States Patent (USP) 6,406,540] propose to relate to by heating NH 4the chemical gas phase reaction process of gallium metal is heated in the steam that Cl is formed.The people such as Wang [J.Crystal Growth 286,50 (2006)] and people's [U.S. Patent application 2007/0142204,2007/0151509 and 2007/0141819] such as Park also discuss methods involving, these are incorporated to herein all by reference of text.The major impurity observed is oxygen, and content is about 16 to about 160ppm.Do not point out the chemical species of oxygen.Tsuji [U.S. Patent application 2008/0193363] discloses to relate to and only heats in ammonia and produce the substitution technique of oxygen level lower than the gan powder of 0.07wt%, and it is incorporated to herein by reference of text.The people such as Spencer [United States Patent (USP) 7,381,391] also disclose to relate to and make Ga metal and wetting agent contact as Bi and in ammonia, only add the another kind of substitution technique of thermogenesis oxygen level lower than the gan powder of 650ppm.
Low cost manufacture that required is is applicable to the crystal growth of bulk gallium nitride crystal and is unfavorable for the method for polycrystalline nitride material of impurity in bulk crystals.
Summary of the invention
According to the present invention, provide the technology about process crystal growth material.More particularly, the invention provides the crystal nitride material being suitable for use as the raw material carrying out the crystal growth containing gallium nitride crystal with ammonia alkali or propylhomoserin technology, also can comprise other aspects.In other embodiments, the invention provides the method being suitable for synthesised polycrystalline nitride material, but will be appreciated that other crystal and material can be processed.This crystal and material include but not limited to GaN, AlN, InN, InGaN, AlGaN and AlInGaN, and other are for the manufacture of the material of block or patterned substrate.These blocks or patterned substrate can be used for multiple application, comprise photoelectric device, laser apparatus, photodiode, solar cell, photoelectrochemistry hydrogen production by water decomposition and hydrogen power generation, photodetector, unicircuit and transistor and other equipment.
In specific embodiments, the invention provides a kind of composition of material.Described composition comprises the polycrystalline III metal nitride materials with multiple crystal grain.Preferably, the feature of described multiple crystal grain is columnar structure.In one particular embodiment, one or more crystal grain has the median size of about 10 nanometers to about 1 millimeter.The atomic fraction of described III metal composition in III metal nitride is about 0.49 to about 0.55.In one or more embodiment, the metal in III metal nitride is at least selected from aluminium, indium or gallium.Described composition also have as III metal oxide or as the oxygen level in III metal nitride materials of the replacement impurity in III metal nitride for being less than about 10ppm.
Replace in particular at one, the invention provides a kind of method forming crystalline material.Described method is included at least one crucible and provides III metal.Preferably, III metal comprises at least one metal be at least selected from aluminium, gallium and indium.Described method comprises providing getter relative to the content of III metal at least 100ppm.In specific embodiments, getter is at least selected from alkaline-earth metal, scandium, titanium, vanadium, chromium, yttrium, zirconium, niobium, rare earth metal, hafnium, tantalum and tungsten.Described method also comprises and the III metal in crucible and getter being provided in chamber.Chamber is heated to determines temperature in described method transfer nitrogenous material to chamber.Described method also comprises chamber to be pressurized to be determined pressure and uses III metal treatment nitrogenous material in the chamber.In one or more embodiment, described method at least forms polycrystalline III metal nitride in containing the crucible of III metal.
Replace in particular at another, the invention provides the substitution technique forming III metal nitride substrate.Described method comprises provides III metal as raw material, and it comprises at least one metal being at least selected from aluminium, gallium and indium.Described method comprises provides getter with the content being at least 100ppm relative to III raw metal, and III raw metal and getter is provided in chamber.Described method also comprises shifting in nitrogenous material to chamber and being heated to by chamber determines temperature.In a preferred embodiment, described method also comprises chamber to be pressurized to and determines pressure and use III raw metal process nitrogenous material in the chamber.In one or more embodiment, described method forms crystal III metal nitride, is characterized as wurtzite structure, substantially not containing any cubic structure composition, is about 2cm at about 385 nanometers to the photoabsorption coefficient of the wavelength of about 750 nanometers -1below.
In addition, the invention provides nitrogen gallium crystal.This crystal has crystalline substrate component, and described crystalline substrate component length is greater than about 5 millimeters, and has the basic wurtzite structure being characterized as and substantially not containing other crystalline structure.In a preferred embodiment, other structure is less than 1 volume % relative to the volume of main wurtzite structure.Crystal also has and is greater than 10 15cm -1the impurity concentration of at least one of Li, Na, K, Rb, Cs, Mg, Ca, F and Cl, and be about 2cm at about 385 nanometers to the photoabsorption coefficient at the wavelength place of about 750 nanometers -1below.
The present invention is used to obtain the advantage surmounting existing technologies.Specifically, the present invention can manufacture the crystal of the starting raw material as high quality nitrogen gallium crystal by cost effectively.In specific embodiments, the inventive method can operate together with steel pipe with the relative assembly simply effectively manufactured with cost such as pottery with equipment.Particular also utilizes the getter material being applicable to process the one or more of chemical for the manufacture of high-quality gallium nitride starting raw material.Depend on embodiment, equipment of the present invention and method can utilize and be prepared according to the conventional material of those skilled in the art and/or method.In preferred embodiments, final crystalline structure is substantially clear and does not have mist degree and other less desirable characteristics.Depend on embodiment, one or more these advantages can be obtained.These and other advantages especially hereinafter can describe at this specification sheets.
The present invention obtains these advantages and other advantages on the basis of known treatment technology.But, will more clearly recognize essence of the present invention and advantage by reference to the specification sheets of following part and accompanying drawing.
Accompanying drawing explanation
Fig. 1,2 and 3 is schematic diagram that reactor is according to embodiments of the present invention described;
Fig. 4 is the simplified flow chart of the synthetic method according to one embodiment of the invention; With
Fig. 5 is the simplified flow chart of the using method according to one embodiment of the invention.
Embodiment
According to the present invention, provide and relate to the technology of process for the material of crystal growth.More specifically, the invention provides the crystal nitride material being suitable for use as the raw material carrying out the crystal growth containing gallium nitride crystal with ammonia alkali or propylhomoserin technology, also can comprise other aspects.In other embodiments, the invention provides the method being suitable for synthesised polycrystalline nitride material, but will be appreciated that other crystal and material also can be processed.This crystal and material include but not limited to GaN, AlN, InN, InGaN, AlGaN and AlInGaN, and other are for the manufacture of block or patterned substrate.These blocks or patterned substrate can be used for multiple application, comprise photoelectric device, laser apparatus, photodiode, solar cell, photoelectrochemistry hydrogen production by water decomposition and hydrogen power generation, photodetector, unicircuit and transistor and other equipment.
The present invention includes the embodiment that can relate to crystalline composition.The present invention includes the embodiment that can relate to the equipment manufacturing crystal composition.The present invention includes the embodiment that can relate to the method manufacturing and/or use described crystalline composition.
As used in specification sheets and claim, approximate language can be used for modifying any expression quantitatively, and it can allow to change and can not cause the change of relative basic function.Therefore, can not be restricted to by the value of modifying as term " about " as described in exact value.In at least one situation, the change that term is about indication can be determined according to the tolerance range of surveying instrument.Similarly, " do not contain " and can be combined with term; Unsubstantiality numeral or trace can be comprised, but still not think and contain modified term, except as otherwise noted.
According to one embodiment of the invention, provide the composition of polycrystalline metal nitride.Described polycrystalline metal nitride can have multiple crystal grain, and these crystal grain can have columnar structure.In some embodiments, a lot of crystal grain can formation polycrystalline block adhered to one another.In other embodiments, the crystal grain of lesser amt can formation polycrystal powder bonded to each other.
With reference to crystal grain, crystal grain can have one or more of characteristic.Characteristic can comprise grain-size.Other characteristics can comprise the mutual angle of inclination of the average number of per unit volume, intercrystalline flexural strength or intercrystalline.
Grain-size can refer to average grain size or average crystal grain diameter.Crystal grain can have columnar structure; In this case, main shaft can be had, and average grain size refers to the mean length of crystal grain along main shaft.Can by one or more minor axis perpendicular to main shaft, the mean diameter of each crystal grain can be determined relative to minor axis.Generally speaking, the mean diameter of each crystal grain can gather with average to form average crystal grain diameter.Described on average refer to mean value herein.
The average grain size of polycrystalline metal nitride can be and is greater than about 10 nanometers.In one embodiment, average grain size can be about 0.01 micron to about 1 millimeter, and in certain other embodiments, grain-size can be about 0.01 micron to about 30 microns, about 30 microns to about 50 microns, about 50 microns to about 100 microns, about 100 microns to about 500 microns, about 500 microns to about 1 millimeter or be greater than about 1 millimeter.Average crystal grain diameter can be and is greater than about 10 microns.In one embodiment, average crystal grain diameter can be about 10 microns to about 20 microns, about 20 microns to about 30 microns, about 30 microns to about 50 microns, about 50 microns to about 100 microns, about 100 microns to about 500 microns, about 500 microns to about 1 millimeter or be greater than about 1 millimeter.
The crystal grain average number of the per unit volume of crystal composition can be expressed as the average or granularity of crystal grain.Composition can have the per unit volume crystal grain average number being greater than about 100/ cubic centimetre.In one embodiment, per unit volume crystal grain average number can be about 100/ cubic centimetre to about 1000/ cubic centimetre, about 1000/ cubic centimetre to about 10,000/ cubic centimetre, about 10, and 000/ cubic centimetre to about 10 5/ cubic centimetre, or be greater than about 10 5/ cubic centimetre.
Crystal grain can each other with the angular orientation determined.Described orientation can be described as pitch angle, can be and is greater than about 1 degree.In one embodiment, grain orientation or pitch angle can be about 1 degree to about 3 degree, about 3 degree to about 5 degree, about 5 degree to about 10 degree, about 10 degree to about 15 degree, about 15 degree to about 30 degree, or are greater than about 30 degree.
Intrinsic or specific characteristic for the one or more crystalline articles produced according to embodiment of the present invention can comprise complete intensity, density, moisture resistivity, porosity etc.Characteristic can utilize corresponding ASTM standard testing to measure.The example of ASTM standard testing can comprise ASTM C 1499.
The intercrystalline flexural strength of the film containing one or more of crystal can be and is greater than about 20 MPas (MPa).In one embodiment, intercrystalline flexural strength can be about 20 MPas and to about 90 MPas, or is greater than about 90 MPas to about 80 MPas, about 80 MPas to about 75 MPas, about 75 MPas to about 70 MPas, about 70 MPas to about 60 MPas, about 60 MPas to about 50 MPas, about 50 MPas.Flexural strength can point out crystal grain-crystal grain relation and/or the intercrystalline intensity of intercrystalline interface.
The apparent density of crystalline articles can be greater than about 1 gram/cc (g/cc).In one embodiment, density can be about 1 gram/cc to about 1.5 grams/cc, about 1.5 grams/cc to about 2 grams/cc, about 2 grams/cc to about 2.5 grams/cc, about 2.5 grams/cc to about 3 grams/cc, or is greater than about 3 grams/cc.Crystalline composition density can be the function of such as porosity or its relative aspect, crystal packing arrangements etc.
Crystalline articles can be aluminium nitride and under standard test condition, has the apparent density being less than about 3.26 grams/cc.In one embodiment, aluminium nitride crystalline articles can have about 3.26 grams/cc to about 2.93 grams/cc, about 2.93 grams/cc to about 2.88 grams/cc, about 2.88 grams/cc to about 2.5 grams/cc, about 2.5 grams/cc to about 1.96 grams/cc, or is less than the apparent density of about 1.96 grams/cc.
Crystalline articles can be gan and under standard test condition, has the apparent density being less than about 6.1 grams/cc.In one embodiment, gallium nitride crystal goods can have about 6.1 grams/cc to about 5.49 grams/cc, about 5.49 grams/cc to about 4.88 grams/cc, about 4.88 grams/cc to about 4.27 grams/cc, about 4.27 grams/cc to about 4 grams/cc or be less than the apparent density of about 4 grams/cc.
The porosity of polycrystalline composition can be and is less than about 30 volume %.In one embodiment, porosity can be about 30% to about 10%, about 10% to about 5%, about 5% to about 1%, about 1% to about 0.1%, or is less than about 0.1 volume %.
The metal of metal nitride can comprise III metal.It is one or more of that suitable metal can comprise in aluminium, gallium or indium.Described " one or more of " can comprise the combination of metal in metal nitride, also can comprise the composition of such as aluminium gallium nitride alloy (AlGaN), InGaN (InGaN), aluminum indium nitride (AlInN), aluminum indium gallium nitride (AlInGaN) etc.
In metal nitride, the mark of metal may be selected to be and not have excess metal in metal nitride.In one embodiment, the atomic fraction of metal can be greater than about 49%.In another embodiment, atomic fraction can be about 49% to about 50%, about 50% to about 51%, about 51% to about 53%, about 53% to about 55%, or is greater than about 55%.
In some embodiments, III metal nitride comprises powder.The grain-size of powder can be 0.1 micron to about 100 microns.Some powder grains can comprise monocrystalline.Some powder grains can comprise at least two crystal grain.In other embodiments, III metal nitride comprises particle.The grain-size of particle can be about 100 microns to about 10 millimeters.Some particle crystal grain can comprise monocrystalline.Some particle crystal grain can comprise at least two crystal grain.
Nitride metal compositions can contain one or more of impurity.As used herein with as conventional in this area, term " impurity " refers to the chemical substance being different from the III metal nitride forming most of polycrystalline metal nitride composition.The impurity of several types can be distinguished according to chemistry, atomic structure, intention and effect.Impurity generally comprises the element being different from nitrogen, aluminium, gallium and indium, comprises oxygen, carbon, halogen, hydrogen, basic metal, alkaline-earth metal, transition metal and primary area metal.The various ways that impurity can have different atomic structure exists.In some cases, impurity exists, such as, as displacement or interstitial impurity with the atom of the separation in the lattice of III metal nitride or ion.In other cases, impurity with not homophase existence, such as, exists as the inclusion in single III metal nitride crystal grain or in the grain boundary of IH race metal nitride.Impurity carefully can add the characteristic strengthening III metal nitride in some respects, or can be not intended to and be.Finally, impurity can have or not have the unusual effect of the electronics of III metal nitride, crystallization, chemistry or mechanical characteristics.
As used herein with as conventional in this area, term " doping agent " refers to the impurity of atomic dispersion in III metal nitride, such as, as displacement or interstitial impurity, and normally has a mind to add.For doping agent and doping precursor (as being generically and collectively referred to as " doping agent " without specializing), the electrology characteristic of III metal nitrogen agent composition controls by adding one or more of this doping agent in the course of processing in above-mentioned composition.Doping agent also can be III nitride metal compositions and provides magnetic and/or fluorescent characteristic.Suitable doping agent can comprise one or more of s or p-block element, transition metal and rare earth element.Suitable s or p-block element can comprise in such as silicon, germanium, magnesium or tin one or more.Other suitable doping agents can comprise one or more transition metals.Suitable transition metal can comprise in such as zinc, iron or cobalt one or more.Suitable doping agent can produce N-shaped material, p-type material or semi-insulating shaped material.In some embodiments, to have a mind to or the oxygen that is not intended to add can be used as doping agent.
Concentration of dopant content suitable in polycrystalline composition can be greater than about 10 10atom/cubic centimetre.In one embodiment, concentration of dopant can be about 10 10atom/cubic centimetre is to about 10 15atom/cubic centimetre, about 10 15atom/cubic centimetre is to about 10 16atom/cubic centimetre, about 10 16atom/cubic centimetre is to about 10 17atom/cubic centimetre, about 10 17atom/cubic centimetre is to about 10 18atom/cubic centimetre, about 10 18atom/cubic centimetre is to about 10 21atom/cubic centimetre, or be greater than about 10 21atom/cubic centimetre.
As used herein, term " getter " refer to have a mind to add and the major metal configuration example had than composition if gallium is for the impurity of the impurity do not expected higher chemical affinity as oxygen has.Getter can the form of inclusion such as metal nitride, metal halide, metal oxide, metal oxyhalide or metal oxynitride be incorporated in polycrystalline III metal nitride.The example of suitable getter comprises alkaline-earth metal, scandium, titanium, vanadium, chromium, yttrium, zirconium, niobium, rare earth metal, hafnium, tantalum and tungsten, and their nitride and halogenide.In some embodiments, getter impurity can be used as getter and doping agent, such as magnesium.In other cases, getter impurity atoms has the atom larger than gallium or the diameter of covalent linkage, and can not be introduced as there is enough content doping agent significantly to change the electrology characteristic of III metal nitride, therefore mainly or be completely used as getter.The amount of getter in polycrystalline III metal nitride can be greater than 100ppm, about 100ppm to about 200ppm, about 200ppm to about 500ppm, about 500ppm to about 0.1%, about 0.1% to about 0.2%, about 0.2% to about 0.5%, about 0.5% to about 2%, about 2% to about 10% or be greater than 10%.Except as otherwise noted, 1,000,000/(ppm) and " % " refer to weight ratio.
In other cases, impurity is not intended to and/or less desirable inclusion in polycrystalline III metal nitride, can from such as processing and processing.Other are not intended to impurity can from the pollution of raw material.Some are not intended to impurity can be relevant with selection raw material more closely.In some embodiments, be not intended to impurity be included in polycrystalline III metal nitride with higher than the aequum alternatively oxygen that exists of impurity or doping agent.In other embodiments, be not intended to impurity comprise with III oxide compound inclusion compound as Ga 2o 3, Al 2o 3, and/or In 2o 3the oxygen existed.Be not intended to that oxygen impurities can be derived from residual oxygen in raw metal, the moisture that exists with the impurity in the phase feed used in synthetic method or O 2, the degasification of reactor parts produces in synthetic method process moisture, or be derived from the air leaking of reactor.In one embodiment, with Ga in gan 2o 3or the oxygen level replacing impurity existence can be less than about 10ppm.In another embodiment, with Ga in gan 2o 3or the oxygen level replacing impurity existence can be about 10ppm to about 3ppm, about 3ppm to about 1ppm, about 1ppm to about 0.3ppm, about 0.3ppm to about 0.1ppm, or be less than about 0.1ppm.
With reference to the equipment comprising embodiment of the present invention, equipment can comprise subsystem such as shell, one or more source of supply and Controlling System.
Shell can comprise one or more wall, assembly etc.The wall of shell can be made up of metal, refractory materials or metal oxide.In one embodiment, the wall of shell comprises at least one in fused quartz, aluminum oxide, carbon or boron nitride.In one embodiment, the shell outer wall that can have inwall and separate with inwall.The internal surface of inwall can limit chamber.
The wall of shell can carry out arranging (such as shape or size) according to processing conditions and required end-use.Configuration can be depending on size and the quantity of assembly, and those assemblies relative position in the chamber.Chamber can have pre-determined volume.In one embodiment, shell can be the cylindrical of the external diameter with about 5 centimetres to about 1 meter and about 20 centimetres to about 10 meters long.Shell can content or vertically lengthen.The orientation lengthened can affect one or more machined parameters.Such as hereafter by what discuss in detail, for content arrangement, a series of crucible can arranged in series make reactant flow flow to another from a crucible.In this arrangement, the concentration of first crucible of series connection and the reactant flow of last crucible in series connection and form can be different.Certainly, this situation can solve along with the change of the configurations such as the rearranging of such as crucible, the redirecting of reactant flow, multiple reactant flow entrances.
Liner can be placed along the periphery of chamber at the internal surface of inwall.Suitable cushioning material can comprise graphite or metal, and liner and other internal surfaces cannot be the sources of less desirable pollutent.Liner can stop or reduce the deposition of material at the internal surface of inwall.Liner can stop or reduce the halogenide of getter metal to the etching of the wall of shell.If can not prevent deposition of material, then liner is removable thus deposition material is peeled off from inwall in cleaning process or change in liner process.
Because inwall can be concentric and spaced apart with outer wall, interval can form path between the inner walls and the outer and flow through wherein for environmental control fluid.The suitable environmental control fluid that can be recycled can comprise rare gas element.Environmental control fluid can comprise gas, liquid or supercutical fluid.Environmental Kuznets Curves entrance extends to interval by outer wall.Available valve stop environmental control fluid to flow through entrance and inlet passage to circulate between the inner walls and the outer.In one embodiment, entrance can be a part for the recycle system, and it can heat and/or cooling environment controls fluid and it can be fluid and provides prime mover.The recycle system can be connected with Controlling System and respond it.Flange, as device used in vacuum system, the leakproof that can provide access connects.
Suitable casing assembly can comprise such as one or more entrance (as feed(raw material)inlet and doping agent entrance), outlet, strainer, heating unit, cooling stave, pressure-responsive structure, crucible and sensor.Some parts can be connected on one or more wall, some can be passed through wall extend with chamber, even if when body seal.Entrance and exit can comprise valve further.
Entrance and exit can be made up of material such as the electropolishing stainless material being suitable for semiconductor manufacturing.Entrance and/or outlet can be welded to corresponding wall, or are fixed on wall by this one or more of metal to metal seal.Optionally, entrance and/or outlet can comprise scavenging agent.In one embodiment, scavenging agent comprises the getter material of such as zirconium alloy, and it can form corresponding nitride, oxide compound and carbide to pollutant reaction, thus reduces the probability polluted in final product.In one embodiment, scavenging agent can be placed in the entrance entering chamber.For the reaction utilizing a large amount of ammonia, the main pollution paid close attention to can be the existence of the water that the moisture-absorption characteristics due to ammonia produces.Ammonia pollution from ammonia tank can be multiplied along with ammonia tank turned letter, when reaching 70% ammonia, and replaceable tank.Or, point (point-of-use) scavenging agent can be used at entrance.Use some scavenging agent can contribute to controlling the pollution of ammonia thus reduce ammonia loss.Optionally, with some scavenging agent can use more low-grade ammonia with needed for obtaining about 99.9999% grade.
The shape of adjustable inlet and outlet or structure are with the flowing through fluid of impact and control flow check.Such as, the internal surface of inlet/outlet can have internal thread (rifled).Internal thread can make gas rotating flow out through end and strengthen mixing.In one embodiment, entrance can connect together make reactant arrival reaction zone or hot-zone before can pre-mixing.Each entrance and exit can have the internal surface limiting gap, can flow into or flow out described chamber through described gap.Valve gap can be adjusted to complete shut-down from standard-sized sheet thus can control fluid and flow through entrance and exit.
Entrance can be adjusted to and promotes the nitrogenous gas of crucible upstream and the mixing of halogen-containing gas, thus promotes the even processing conditions of whole chamber volume.In order to promote mixing, one or more entrance can contain one or more baffle plate, gap, frit etc.Described gap, frit and baffle plate can be placed in chamber and move to control chamber air flow closest to hot-zone or crucible, and this can stop or reduce the formation of solid ammonium halide as far as possible.Described gap, frit and baffle plate can be placed in the upstream closest to crucible, and spacing distance is about 2cm to about 100cm, mixes for completing before starting to react with the content in crucible.The existence of gap and baffle plate can promote higher gas flow, and its promotion mixes and suppresses gas backstreaming, stops or reduce as far as possible the formation of solid ammonium halide.
One or more crucible can be placed in chamber.In one embodiment, the crucible quantity in chamber is about 6.Depend on the configuration of chamber, crucible can content and/or arranged vertically in chamber.Crucible shape and size can pre-determine based on the terminal use of metal nitride, type of feed and processing conditions.For the polycrystalline composition being used as sputtering target, the desired size of the comparable sputtering target of size of crucible is relatively large.The redundance of polycrystalline composition removes to form sputtering target goods by such as etching or excision.Thisly remove the surface contamination can eliminated and contact with crucible material and produce.
Crucible can tolerate and form temperature required temperature higher than crystalline composition and simultaneously holding structure integrity and unreactiveness.This temperature can be higher than about 200 degrees Celsius, is about 200 degrees Celsius to about 1200 degrees Celsius, or higher than about 1200 degrees Celsius, therefore, refractory materials is adapted at using in crucible.In one embodiment, crucible can comprise the fire proofing composition containing oxide compound, nitride or oxynitride.Crucible can be formed by one or more in graphite, molybdenum, tungsten or rhenium, or is formed by one or more in the oxide compound of silicon, aluminium, magnesium, boron or zirconium, nitride or oxynitride.In a preferred embodiment, crucible is formed by non-oxidic material such as boron nitride, silicon carbide, tantalum carbide or carbon material such as graphite.In one embodiment, a kind of removable graphite backing can be placed in crucible and be beneficial to easily remove polycrystalline composition.In some embodiments, getter adds in crucible with the form of thin slice or liner.In one particular embodiment, in getter thin slice or liner selected among zirconium, hafnium and tantalum one of at least.In another embodiment, crucible composition comprises at least one getter.
A certain amount of III metal containing at least one in aluminium, gallium and indium can be placed at least one crucible.III metal can solid or liquid form add.At least one crucible can be placed in together with III metal with the getter of at least one in tungsten containing alkaline-earth metal, scandium, titanium, vanadium, chromium, yttrium, zirconium, niobium, rare earth metal, hafnium, tantalum.Getter can be greater than 100ppm relative to the weight of III metal, is greater than 300ppm, is greater than 0.1%, is greater than 0.3%, is greater than 1%, is greater than 3%, or the content being greater than 10% adds.Getter can powder, coarse grain, silk or sheet form add.Getter can metal, nitride, halogenide or its compound or compound form adds, getter can comprise oxygen.
In one embodiment, at least one wetting agent add in crucible with III metallic contact." wetting agent " used herein refers to simple substance or the compound of mixing and the reaction contributed in the interface of two assemblies between incompatible liquid mixture.Wetting agent can be any contribute to the boundary moisture of biliquid metal mixture metal and be not easy to reaction to form covalent linkage with III element.Any suitable and effective wetting agent compound can be used.Suitable wetting agent comprises bismuth (Bi), plumbous (Pb), germanium (Ge) and tin (Sn).Other suitable wetting agents comprise antimony (Sb), tellurium (Te) and polonium (Po).Reaction mixture also can comprise the mixture of two or more wetting agents of arbitrary proportion.Reaction mixture can comprise a kind of wetting agent, such as, organometallic compound containing wetting agent metal or the mineral compound containing wetting agent metal.Suitable wetting agent compound comprises such as halogenide, oxide compound, oxyhydroxide and nitrate.Much suitable and effective wetting agent and wetting agent compound are disclosed in such as Aldrich Handbook of Fine Chemicals, 2003-2004 (Milwaukee, Wis.).As used herein, bismuth, germanium, tin and lead refer to elemental metals, the alloy containing these metals, the compound containing these metals, and composition thereof.III metal and wetting agent can the mol ratio of about 1: 1 to about 500: 1 exist.Particularly, III element and wetting agent can about 2: 1, about 5: 1, about 20: 1, about 100: 1 or about 200: 1 mol ratio exist.
Suitable sensor can comprise in pressure transmitter, temperature sensor and gas composition sensor one or more.Sensor can be placed in chamber, and the machined parameters in chamber can be communicated with Controlling System.
Suitable source of supply can comprise in energy source, nitrogenous gas source, carrier gas source, halogen-containing gas source, raw material source (sometimes referring to holder), environmental control fluid source etc. one or more.
Energy source can be positioned near shell, and by wall to chamber supplying energy, as heat energy, plasma energy or ionization energy.Energy source can be used as supplementing of above-mentioned heating unit or replaces and exist.In one embodiment, energy source can extending towards outer surface along the outer wall of shell.Energy source can be chamber and provides energy.
Energy source can be source of microwave energy, thermal energy source, plasma source or laser source.In one embodiment, heat energy can be provided by well heater.Suitable well heater can comprise molybdenum heater, splits formula stove well heater, 3rd district split in formula stove or induction heater one or more.
Sensor can be placed in chamber.Sensor can tolerate the pressure of high temperature in chamber and rising or reduction, and is chemically inert.Sensor can be placed near crucible place, and/or can be placed in ingress.Sensor can detect processing conditions as the temperature in chamber, pressure, gas composition and concentration.
Nitrogenous gas source is by the first entrance and chamber.Nitrogenous gas source can comprise one or more strainer, scavenging agent or moisture eliminator with purification and/or dry nitrogenous gas.In one embodiment, nitrogenous gas can manufacture in source.The purification content of nitrogenous gas can keep meeting or exceeding semi-conductor purifying grade standard by scavenging agent.Suitable nitrogenous gas can comprise ammonia, diatomic nitrogen etc.If the existence of carbon is not a problem, then itrogenous organic substance can be used.
The gap controlling related valves can control nitrogenous gas to the flow in chamber.Except as otherwise noted, flow refers to volumetric flow rate.The consideration, sample size etc. of processing can determine suitable gas flow.The flow of nitrogenous gas can be greater than about 10 (standard) cc/min.In one embodiment, the flow of nitrogenous gas can be about 10 cc/min to about 100 cc/min, about 100 cc/min are to about 200 cc/min, about 200 cc/min are to about 500 cc/min, about 500 cc/min are to about 1200 cc/min, about 1200 cc/min are to about 2000 cc/min, about 2000 cc/min are to about 3000 cc/min, about 3000 cc/min are to about 4000 cc/min, about 4000 cc/min are to about 5000 cc/min, or be greater than about 5000 cc/min.In some embodiments, the flowing of the nitrogenous gas in unit volume per minute is chosen as 1.5 times of the volume of III metal.In some embodiments, nitrogenous gas stream flows on III metallic surface with the gas flow of at least 0.1 cel, and temperature of reaction is at least 700 degrees Celsius and is no more than 1,200 degrees Celsius.
Carrier gas source is by entrance and chamber or share the first entrance with nitrogenous gas.Nitrogenous gas can be diluted to carrier gas pre-mixing nitrogenous gas and determine content.Because nitrogenous gas can be used as the carrier gases dilute of inertia, the possibility forming some halogenide solid at the first access point closest to chamber reduces.Suitable carrier gas can comprise in argon gas, helium or other rare gas elementes one or more.In one embodiment, carrier gas inlet is set to carrier gas stream can affect the nitrogenous gas stream being present in the first entrance.In one embodiment, doping agent can be carried secretly to be used as the inclusion of polycrystalline composition in carrier gas.
Halogen-containing gas stream is by the second entrance and chamber.As nitrogenous gas source, halogen-containing gas source can comprise one or more strainer, scavenging agent and moisture eliminator etc., therefore can at the purification of source place and/or dry halogen-containing gas.Halogen ferritic can manufacture in source.Suitable halogen-containing gas can comprise hydrogenchloride etc.In some embodiments, technique can omit halogen-containing gas.
The gap controlling related valves can control halogen-containing gas to the flow in chamber.The consideration, sample size etc. of processing can determine suitable gas flow.The flow of halogen-containing gas can be greater than about 10 (standard) cc/min.In one embodiment, the flow of halogen-containing gas can be about 10 cc/min to about 50 cc/min, about 50 cc/min are to about 100 cc/min, about 100 cc/min are to about 250 cc/min, about 250 cc/min are to about 500 cc/min, about 500 cc/min are to about 600 cc/min, about 600 cc/min are to about 750 cc/min, about 750 cc/min are to about 1000 cc/min, about 1000 cc/min are to about 1200 cc/min, or be greater than about 1200 cc/min.
Halogen-containing gas can flow into chamber from halogen-containing gas source through the second entrance.As nitrogenous gas, halogen-containing gas can be diluted to carrier gas pre-mixing halogen-containing gas determines content.Available inert carrier gas dilution halogen-containing gas second ingress that can be reduced in closest to chamber forms the possibility of some halogenide solid.Suitable carrier gas can comprise in argon gas, helium or other rare gas elementes one or more.Optionally, carrier gas inlet can be set to carrier gas stream can affect the halogen-containing gas stream being present in the second entrance or having entered chamber.In one embodiment, doping agent can be carried secretly to be used as the inclusion of polycrystalline composition in carrier gas.
Halogen-containing gas and nitrogenous gas can determine that the mode of the characteristic of polycrystalline composition is introduced in chamber.Introduce when described mode can be included in the full flow of each component flow (gas, liquid or supercritical liq) simultaneously.Other suitable incorporation way can comprise pulse and introduce one or more components, change the concentration of one or more components and/or flow or staggered introducing and such as use carrier gas wash chamber.
Halogen-containing gas and nitrogenous gas entrance can be set to the hot-zone that exit end is positioned at chamber.In one embodiment, therefore the region that one or more entrance is positioned at chamber in use has the temperature higher than about 341 degrees Celsius at one atm, or is about 341 degrees Celsius to about 370 degrees Celsius, or higher than about 370 degrees Celsius.
The flow of adjustable nitrogenous gas reacts to optimize with the ratio of the flow of halogen-containing gas.In one embodiment, the flow of nitrogenous gas and the ratio of the flow of halogen-containing gas can be about 30: 1 to about 15: 1, about 15: 1 to about 1: 1, about 1: 1 to about 1: 10, or about 1: 10 to about 1: 15.
Raw material source is communicated to the crucible being arranged in chamber by feed(raw material)inlet.As other sources, raw material source can comprise strainer, moisture eliminator and/or scavenging agent.Especially with reference to raw material source, the purification of the raw material of supply can have out-of-proportion large impact or effect to the characteristic of final polycrystalline composition.Raw material can be produced before use or can be kept in an inert atmosphere to reduce as far as possible or to suppress the pollution relevant with atmosphere.Such as, if use hygroscopic materials or be easy to form the material of oxide compound, then raw material can be processed and/or store to make raw material not contact with moisture or oxygen.In addition, in one embodiment, due to indoor at course of processing Raw melting inflow chamber, therefore can use different material in successive processes, this is more feasible relative to interval type process.Following discloses this difference of at least some.
Suitable raw material can comprise one or more of gallium, indium or aluminium.In one embodiment, raw material can have the purity of 99.9999% or higher.In another embodiment, purity can be greater than about 99.99999%.Raw material can be gas, liquor, suspension or slurry; Or molten solids.Oxygen remaining in metal by under such as hydrogen reducing atmosphere or heating under vacuum reduce further.
In one embodiment, the material needed for all production can seal in the chamber in operation; And in another embodiment, various material can be added in treating processes.Such as, raw material can flow through feed(raw material)inlet, out enters into crucible from exit end.If any multiple crucible, an entrance that can use multiple feed(raw material)inlet or have multiple exit end makes raw material flow into each crucible.In one embodiment, feed(raw material)inlet can be arranged on the feeding structure of motion of translation.This feeding structure can make the exit end of feed(raw material)inlet be transformed into another crucible from a crucible.
Raw material controls to the flowing through feed(raw material)inlet of the flowing of feed(raw material)inlet and flow and raw material and flow by valve.Valve can respond the control signal from Controlling System.Although the flow of raw material can be determined based on application-specific parameters, suitable flow can be greater than about 0.1 kg/hr.In one embodiment, flow can be about 0.1 kg/hr to about 1 kg/hr, about 1 kg/hr to about 5 kgs/hr, or is greater than about 5 kgs/hr.
Doping agent entrance can with storer and the chamber containing doping agent.Storer can be made up of the material meeting semiconductor grade standard.Storer can provide purification/dry doping agent.In one embodiment, storer can have liner.Described liner can prevent the corrosion of storage material, or reduces the possibility that doping agent is stored device pollution.
In the course of processing, dopant source can separate with one or more other materials added or jointly locate.If added separately, doping agent can provide the port leaving doping agent entrance to flow directly into crucible.As previously mentioned, doping agent is by such as introducing with raw material, carrier gas, halogen-containing gas or nitrogenous gas pre-mixing.The metering of doping agent can control the concentration of dopant content in polycrystalline composition.Similarly, the layout of the doping agent in polycrystalline composition obtained by the interpolation time of such as pulse, circulation or doping agent.
Suitable doping agent can comprise dopant precursor.Such as, silicon can as SiCl 4introduce.If carbon is required doping agent, carbon can as hydrocarbon polymer as methane, methylene dichloride or tetracol phenixin be introduced.Suitable doping agent can comprise halogenide or hydride.When carbon be required doping agent or inessential pollutent, metal can be introduced as organometallic compound.Such as, magnesium can as Mg (C 5h 5) 2introduce, zinc is as Zn (CH 3) 2introduce, iron is as Fe (C 5h 5) 2introduce.The flow of dopant precursor can be greater than about 10 (standard) cc/min.In one embodiment, the flow of dopant precursor can be about 10 cc/min and to about 1200 cc/min, or is greater than about 1200 cc/min to about 750 cc/min, about 750 cc/min to about 500 cc/min, about 500 cc/min to about 100 cc/min, about 100 cc/min.Or doping agent can such as add as the form of the alloy of raw material by simple substance.Other suitable doping agents can comprise Si, O, Ge, Be, Mg, Zn, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Mo, Sn, Ce, Pr, Nd, Pm, Sm, one or more in Eu, Dy, Er, Tm, Yb or Hf.
Outlet and corresponding valve can control the release of the material in chamber.The material of release can be discharged into air, or can be captured such as with salvage material.The material of release detects composition and/or temperature by the suitable sensor being arranged on outlet.Sensor can send information to Controlling System.Owing to carrying out decreasing pollution through chamber to the flowing of direction by controlling material, so polycrystalline composition removes from chamber by the export structure of the wall at outlet side.
Outlet can be connected with air-bleed system.Air-bleed system can form lower pressure of foundation or form pressure reduction relative to normal atmosphere in the chamber.Suitable pressure of foundation can be less than about 10 -7millibar.In one embodiment, pressure of foundation can be about 10 -7millibar is to about 10 -5millibar, or be greater than about 10 -5millibar.In one embodiment, pressure reduction can be about 50 holders to about 1 holder, about 1 holder to about 10 -3holder, about 10 -3holder is to about 10 -5holder, or be less than about 10 -5holder.Bleed and can be used for precleaning, or can use in treating processes.
Outlet can be heated to certain temperature and keep, and the pressure that described temperature is greater than when the ammonium halide that may be formed in treating processes is greater than processing pressure as temperature during 1 bar.By on the sublimation temperature that temperature remained on ammonium halide under reaction pressure, ammonium halide can flow in trap maybe can get rid of and formed or once be formed in solidification near outlet.
The treater that Controlling System can comprise controller, be communicated with controller, with the wired or wireless connected system making controller be communicated with sensor, valve, source, monitoring and apparatus for evaluating etc.
Sensor in chamber can condition in Sensing chamber.Such as temperature, pressure and/or gas concentration and composition, and can to controller transmission of signal information.Flow monitor can by the flow information Signal transmissions through corresponding entrance or outlet to controller.Controller (via treater) can respond the information received, and may correspond in information and predict that instrument parameter carrys out control device.Such as, controller can send signal to provide heat energy to chamber to energy source.In the process of polycrystalline composition synthesis, controller sends signal to open, to cut out or be opened to certain flow content can to one or more valve.Programmable logic controller is to implement the method growing polycrystalline composition according to embodiments of the present invention.
Gained polycrystalline composition can be III metal nitride.Metal nitride can be doped to obtain one or more n-and adulterate or p-doped compositions.Metal nitride can be metal, semiconduction, semi-insulating or insulating material.In addition, these compositions can be magnetic or fluorescent material separately.
Below with reference to exemplary, the running of equipment and the function of different assembly are described.With reference to accompanying drawing, exemplary description embodiment of the present invention and the present invention is not limited to this.
Fig. 1 illustrates the equipment 100 according to an embodiment.Equipment 100 can be used for preparing metal nitride materials, can comprise the shell 102 with wall 104.Wall 104 can have the internal surface 106 limiting chamber 108.Energy source 110 can be positioned at closest to wall 104.First entrance 112 and the second entrance 114 extend past wall 104.Entrance 112,114 limits gap, can flow into or flow out chamber 108 by described gap material.Outlet 118 extends to chamber 108 by wall 104.Crucible 120 can be arranged in chamber 108.Liner (not shown) can the internal surface 106 of small pieces of cloth used for patches wall 104.
Energy source 110 can be thermal energy source, as ceramic heater.Entrance 112,114 and outlet 118 can be the electropolishing stainless steel being suitable for semiconductor manufacturing.In specific embodiments, crucible 120 can comprise boron nitride, and inertia liner can comprise graphite.
In operation, III raw metal and getter can be packed into crucible 120, and crucible can be pre-loaded in chamber.One or more doping agents can be placed in crucible together with raw material.After loading, crucible 120 can seal with sealing machine (not shown).
Nitrogenous gas can be passed through the first entrance 112 and flows into chamber 108.Nitrogenous gas can comprise ammonia, and can comprise due to prediluted carrier gas.Halogen-containing gas can be passed through the second entrance 114 and flows into chamber 108.Halogen-containing gas can comprise hydrogenchloride.Halogen-containing gas can use carrier gas pre-dilution.Unreacting gas and/or other waste materials can be passed through outlet 118 and remove from chamber 108.Chamber 108 can be cleaned by making gas flow into through entrance 112,114 and be flowed out by outlet 118 before crystalline composition is formed.Optionally can monitoring stream effluent to monitor the foreign matter content in eluting gas, this can indicate when obtain sufficient cleaning.
Energy source 110 can be activated.Activation energy source 110 can increase and the temperature in chamber 108 risen to predetermined content and improves with preset temperature speed.In chamber 108 and closest to the region of crucible 120, hot-zone or reaction zone (not shown) can be limited.
Raw material in crucible 120, can respond at a certain temperature and contact, to form metal nitride and polycrystalline composition by reacting with nitrogenous gas under halogen-containing gas exists.
Do not wish to be limited to any theory, it is believed that III metal and hydrogen halide react to form volatile III metal halide.III metal halide is transferred with nitrogenous gas such as ammonia gas react to form polycrystalline III metal nitride.Under Typical process conditions, most iii race metal can react and form polycrystalline III metal nitride, only has small portion III metal the form of III metal halide to shift out from crucible.Under type reaction condition, some, most or all getters dissolve in liquid III metal.Disclosed a lot of getter is extensively miscible in liquid aluminium, gallium or indium at higher than the temperature of 500-1000 degree Celsius above.Even if refractory materials Zr, Hf and Ta also can be dissolved in gallium higher than the content of about 1-2% under 1000 degrees Celsius.The metal casing dissolved mixes well in melting III metal.The getter metal dissolved can react with the oxygen that dissolves in melting III metal the oxide compound forming getter metal.As III metal, getter metal can form halogenide and/or nitride.At the temperature of about 500 to 1000 degrees Celsius, getter metal halogenide is relatively volatile, and getter metal nitride, oxide compound and oxynitride are general not volatile.When some getters of such as alkaline-earth metal and yttrium, mainly halogenide can be formed, and most of getter metal shifts out from crucible.But in reaction and transmitting procedure, getter metal effectively fetters or removes the neutralization of III metal and comprises O 2and H 2oxygen in oxygen source in the gas phase of O is when other getters of such as Cr and Ta, mainly nitride can be formed, and most of getter metal the form of nitride, oxynitride and oxide compound inclusion can be stayed in crucible in polycrystalline group III-nitride.Reaction and transmitting procedure in, getter metal effectively fetter or remove in III metal with gas phase in oxygen source in oxygen.
In some embodiments, comprise those do not relate to reaction in add hydrogen halide, most or all getters can be introduced in polycrystalline group III-nitride composition.
After formation crystal composite, shell 102 can be opened at outlet side.Open at outlet side and the pollutent of the introducing chamber 108 caused due to opening can be confined to the side of chamber closest to outlet 118.Pollutent is confined to can reduce the distance of pollutent being cleaned out chamber 108 process closest to outlet 118, and the path of pollutent is limited in the region that wherein pollutent unlikely touches any growing crystal or crystalline composition growth surface (internal surface as crucible 120).In addition, the shell not opening inlet side can be reduced in the possibility of the leakage of close entrance in subsequent action process.Therefore, this configuration contaminant reducing pollutes the chance of the crystal produced.
Fig. 2 illustrates the equipment 200 according to an embodiment.Equipment 200 can comprise shell 202, and the energy source 204 of close shell 202.Shell 202 can comprise inwall 206 and outer wall 208.Entrance 209 can be passed through outer wall 208 and extends, but can be shorter than inwall 206 and stop.Outer wall 208 can have towards outer surface.Inwall 206 can limit chamber 214 towards interior surface or internal surface 212.
Inwall 206 can be embedded in outer wall 208 and to separate with outer wall 208.Interval between wall 206 and 208 can be used for the environmental control fluid entered via the entrance 209 constructed for this purpose in space that circulates.Outer wall 208 can be formed by metal, and inwall 206 can be formed by quartz.Energy source 204 can close to outer wall 208.
First entrance 216, second entrance 218, feed(raw material)inlet 224, doping agent entrance 232 and outlet 226 can be passed through inner and outer wall 206 and 208 and extend.Multiple valve 215,220,223,233 can be arranged on and extends in the feed-pipe of corresponding entrance 216,218,224 and 232 from source in a ground in each pipe.Single feed-pipe does not mark with Reference numeral.Further, export 226 and can have the valve 227 that can allow or stop fluid to flow through.
First entrance 216 can be communicated with nitrogenous gas source 217 and be flowed in chamber 214 by nitrogenous gas.Nitrogenous gas can comprise ammonia.Nitrogenous gas can use carrier gases dilute.Carrier gas can be argon gas, and can come with nitrogenous gas flow point and control.Second entrance 218 can be communicated with halogen-containing gas source 219.Second entrance 218 can allow halogen-containing gas to flow into chamber 214 from halogen-containing gas source 219.Valve 220 can control to flow through the second entrance 218 from the halogen-containing gas in halogen-containing gas source 219 and enter in chamber 214.Halogen-containing gas can comprise hydrogenchloride, and it can by carrier gases dilute.Feed(raw material)inlet 224 can be communicated with raw material storage device 222.The exit end of feed(raw material)inlet 224 can be configured such that the raw material leaving entrance 224 flows in crucible 230.Valve 223 can control to enter in chamber 214 through feed(raw material)inlet 224 from the feedstream of holder 222.Raw material can comprise molten gallium.
Dopant source (not shown) is communicated with chamber 214 by doping agent entrance 232.Valve 233 can flow into chamber 214 with unlatching or prevention doping agent from dopant source by opening/closing.In an exemplary embodiment, doping agent comprises silicon, can be SiCl 4form.
Outlet 226 can allow excess stock to leave chamber 214.Valve 227 can open or cut out, and by closing, can set up back pressure when other materials flows into chamber 214 and temperature rises.
Multiple crucible 230 can be arranged in chamber 214.Crucible 230 can content arrangement each other.Sensor 236 and 237 can be set to monitor the pressure and temperature in chamber 214 or other process parameters.
As mentioned above, environmental control fluid can be passed through in the space that entrance 209 flows between wall.Entrance 209 can be communicated with the recycle system (not shown) fluid in space is between the walls circulated.Entrance 209 can comprise valve 211 with adjustment or the circulation optimizing space between wall.Flange 210 for vacuum system can be used for forming leakproof and connects.Fluid circulating system can supply heating or cooling fluid.Chamber 214, and its content, by this arrangement cooling or heating.
Controlling System can comprise controller 234, and it can with various by being communicated with the members shown in line.By these lines, controller 234 can receive information, such as signal from sensor 236,237.Controller 234 can to the one or more transmission signals in valve 215,220,223,227,233, and valve responds by opening or cutting out.Valve 211 can be communicated with controller 234, and by described valve 211, controller 234 can control environmental control fluid and flow from the recycle system.Therefore, controller 234 can be monitored and can be controlled whole reaction conditions.
Before running, can bleed to chamber 214.Controller 234 can activate valve 227 and vacuum pump (not shown) to bleed to chamber 214.Chamber 214 can rinse with inert carrier gas.Energy source 204 can start to do in order to heating thus any volatilizable pollutent that volatilizees.Continuous air extraction and cleaning can remove pollutent from chamber 214.
In operation, controller can activate valve 223 to start raw material to flow to crucible 230 from holder 222 by feed(raw material)inlet 224.Doping agent can flow into crucible when corresponding to respective valve 233 and opening by doping agent entrance 232.Controller adjusts the flow of material by the degree that adjustment respective valve is opened or closed.Controller 234 can be communicated with sensor 236,237.Temperature and pressure in chamber is promoted to determines content by the controller 234 in activation energy source 204 and/or adjustment outlet valve 227.
Once reach the temperature and pressure of expection, then nitrogenous gas is introduced in chamber 214 by the first entrance 216.Or nitrogenous gas can be introduced in chamber when heating cycle starts.Halogen-containing gas can be passed through the second entrance 218 and flows into.Controller is by controlling each valve 215,220 to adjust the flow of these gases.
The raw material comprising doping agent can react with nitrogenous gas under halogen-containing gas exists.Reaction can proceed to raw material reaction and form metal nitride.In an exemplary embodiment, the gan of silicon doping can be formed.
Fig. 3 describes the schematic diagram according to the equipment 400 of the entrance of embodiment in detail.Equipment 400 can comprise the shell 402 with wall 404, and described wall 404 can have internal surface 406 and towards outer surface 408, as shown in the figure.Wall 404 can be radially spaced with axle 409.Energy source 410 can be provided as near outside surface 408.The internal surface 406 of wall 404 can limit chamber 412.
Equipment 400 also can comprise entrance 416 and 418.In one embodiment, entrance 416 be can be solid wall and is extended in chamber 412 by wall 404.Entrance 416 can to embed in the internal surface 406 of wall 404 and with it and interval.The exit end of entrance 416 can limit gap 422.Baffle plate 424 can press close to gap 422.The internal surface 406 of entrance 416 and wall 404 directly can limit entrance 418 in interval.In addition, gap or opening 426 can be arranged in entrance 418.Crucible 430 can be arranged in chamber 412.
Halogen-containing gas is incorporated in chamber 412 by source (not shown) by entrance 416, and nitrogenous gas is incorporated in chamber 412 by source (not shown) by entrance 418.Entrance 416 and 418 can be configured to the baffle plate 424 arranged in entrance 416 and assist mixing to flow into the gas of chamber 412 by entrance.
Equipment 400 also can comprise not shown parts such as Controlling System, and described Controlling System comprises controller, the adjustment that can control whole reaction and/or controls the sensor that material flows into and/or flow out the flowing of material of chamber, the source that can be flowed into from it by raw material and/or doping agent entrance, raw material and/or the doping agent introduced in chamber chamber, monitoring chamber room temp, pressure and composition.The running of equipment can be explained with reference to above-mentioned embodiment.
Fig. 4 chamber illustrates the schema preparing the method for polycrystalline III metal nitride according to embodiments of the present invention.Described method by providing III metal and getter in crucible.Then the crucible containing III metal and getter to be loaded in chamber or reactor and sealed chamber.Then to chamber evacuation, cleaning or purification to remove trace impurity.Can bleed to chamber, and clean or purify before load III metal and getter wherein.Environmental adjustments in chamber is to predetermined content.Temperature in chamber can be maintained at about 800 degrees Celsius to about 1300 degrees Celsius, and the pressure in chamber can be and is greater than about barometric point
Doping agent can be incorporated in chamber.Doping agent can be used as dopant precursor and introduces.Dopant precursor can flow into chamber from dopant source.
Temperature in chamber can rise to about 800 degrees Celsius to about 1300 degrees Celsius, and pressure can rise at least one dimension and be greater than about 1 meter, and time remaining exceedes about 30 minutes.Then, nitrogenous gas such as ammonia can be introduced in chamber.Gas can flow into chamber from nitrogenous gas source through entrance.The flow of nitrogenous gas can exceed about 250 (standard) cc/min.
Halogen-containing gas can be introduced in chamber.Optionally, the order of preceding step can be exchanged.The flow of halogen-containing gas can be greater than about 25 cc/min.The flow of nitrogenous gas can be about 10: 1 with the ratio of the flow of halogen-containing gas.
III metal can react with nitrogenous gas and form polycrystalline III metal nitride under halogen exists.Halogen affects the reaction between metal and nitrogenous gas in a specific way.Getter and oxygen react and form getter metal oxide compound, oxynitride or oxyhalogenide.And other and nitrogenous gas reacts to form getter metal nitride and react with hydrogen halide and forms getter metal halogenide.
React and continue by vapor transmission and/or wicking action.Metal nitride shell can be formed at the top of molten metal in crucible.Described shell can porous slightly.Metal can by vapor transmission, or if liquid, is reacted by wicking action by hole to the top of shell with nitrogenous gas.Reaction can deposit other metal nitride and add on shell.Reaction proceeds in fact all metals and all passes through reaction.Other metal can flow into chamber from holder.
Chamber can be cooled, for Fig. 5.The nitrogenous gas filtered and hydrogen halide flow out reaction zone, and ammonium halide can in the comparatively cool region condensation of chamber.In one embodiment, outlet can keep heat to promote that the downstream of ammonium halide is caught; Or cold wall portion can be incorporated to promote the condensation of ammonium halide.Chamber can at outlet side opening to be reduced by the leakage of inlet side as far as possible.Polycrystalline III metal nitride removes by outlet side.
Optionally, the polycrystalline III metal nitride of formation can be further processed.In one embodiment, at least one surface of polycrystalline III metal nitride can experience scraping, scrub or one or more in scribing.Surface can experience oxidation in air or dry oxygen further and can boil in perchloric acid further.The amounts of residual contamination obtained by post-processing step by cleaning, ultrasonic or the two jointly remove.Cleaning and ultrasonicly can to carry out in such as organic solvent, acid, alkali, oxygenant (as hydrogen peroxide) etc.Polycrystalline III metal nitride can be annealed in inertia, nitrogenize or reducing atmosphere.Annealing also can carry out the time of about 30 minutes to about 200 hours in pure ammonia at the temperature of about 800 degrees Celsius to about 1200 degrees Celsius.
Other process can be carried out to be used as the source material of crystalline composition growth.In order to be used as source material, polycrystalline III metal nitride can be ground into crystal grain.Crystal grain can have the average diameter range of about 0.3 millimeter to about 10 millimeters.Pulverize break by such as compression fracture, jaw, scroll saw, ball milling, airflow milling, laser cutting or low temperature pressure break carry out.The extraneous metal that rear pulverizing clean operation is removable to be introduced by crushing operation, unreacted metal and the metal oxide do not expected.
In some embodiments, polycrystalline III metal nitride is used as the source material of the ammonia heat growth of at least one group III metal nitride single crystal.Polycrystalline III metal nitride is placed in autoclave or sealed cabin, as United States Patent (USP) 6, and 656,615,7,125,453 and 7,078,731 and U.S. Patent application 12/133, described in 365, it is incorporated to herein these documents in full by reference.Ammonia and mineralizer such as basic metal, acid amides, nitride or nitrine, alkaline-earth metal, acid amides, nitride or nitrine is also placed, at least one in the reaction product between Neutral ammonium fluoride, ammonium chloride, III metal fluoride, III metal chloride or III metal, ammonia, HF and HCl in autoclave or sealed cabin.
In some embodiments, getter is also placed in autoclave or sealed cabin.Except the getter composition that can exist in polycrystalline group III-nitride can provide the getter added.The getter added can comprise at least one in alkaline-earth metal, Sc, Ti, V, Cr, Y, Zr, Nb, Hf, Ta, W, rare earth metal and their nitride, halogenide, oxynitride, oxyhalogenide, acid amides, sub-acid amides and trinitride.In a certain aspects, getter at least partially adds with metallic forms, mineralizer adds with trinitride at least partially, the ratio added be the nitrogen that produces of the hydrogen that produced by getter metal and ammonia and being decomposed by trinitride with about 3: 1 ratio exist, as U.S. Patent application No.61/086, described in 799, this file entirety is incorporated to herein by reference.The getter added can be used for removing the impurity such as oxygen unintentionally existed in mineralizer or other raw materials.In a set of embodiment, mineralizer comprises basic metal, and getter comprises Be, Mg, Ca, Sr, Ba, Sc, Y, rare earth metal, the nitride of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo or W, sub-acid amides or acid amides.In another set of embodiment, mineralizer comprises Cl, and getter comprises the nitride of Sc, Cr, Zr, Nb, Hf, Ta or W, muriate, oxynitride or oxychloride.In a set of embodiment again, mineralizer comprises F, and getter comprises nitride, the fluorochemical of Cr, Zr, Nb, Hf, Ta or W.Oxynitride or oxyfluoride.
After all raw materials add autoclave or sealed cabin, sealing autoclave or sealed cabin.
If application sealed cabin, then sealing cabin is placed in suitable high-tension apparatus.In one embodiment, high-tension apparatus comprises as U.S. Patent No. 7, the autoclave described in 335,262 (being incorporated to by reference of text herein).In another embodiment, high-tension apparatus chamber is as U.S. Patent No. 7, the high-tension apparatus of the inside heating described in 125,453 and U.S. Patent application 2006/0177362A1 and U.S. serial No.12/133,364 (above entirety is incorporated to herein by reference).Then in supercritical ammine, process polycrystalline III metal nitride under higher than the temperature of about 400 degrees Celsius and higher than about 0.2 gpa (GPa) pressure, the etched and recrystallization of polycrystalline III metal nitride has on the group III-nitride crystal of wurtzite structure at least one at least partially in this process.In some embodiments, polycrystalline III metal nitride in supercritical ammine higher than about 500 degrees Celsius, higher than about 550 degrees Celsius, higher than about 600 degrees Celsius, higher than about 650 degrees Celsius, higher than about 700 degrees Celsius or higher than the temperature of about 750 degrees Celsius under process.In some embodiments, polycrystalline III metal nitride in supercritical ammine higher than about 0.3GPa, higher than about 0.4GPa, higher than about 0.5GPa, higher than about 0.6GPa, higher than about 0.7GPa or the pressure higher than about 0.8GPa under measure.
Getter remaining in polycrystalline III metal nitride is progressively discharged in solution along with polycrystalline III metal nitride etches.When in the solution, getter can react and form getter metal nitride, acid amides or halogenide.Getter also can with oxygen chemical bonding.Getter can remove oxygen remaining in supercritical ammonia solution, to grow the group III-nitride monocrystalline having and improve purity.
In some embodiments, the getter added carried out annealing and/or alligatoring before III the metal nitride significantly growth of ammonia heat.In some embodiments, getter can be used as fine powder and adds or under mineralizer exists, can form fine powder in ammonia in heat-processed, and it can to experience in whole environment of crystal growth less desirable convection current and/or merge as inclusion and crystallization III metal nitride.Getter by such as keeping for some time of about 10 minutes to about 48 hours to consolidate at about 200 degrees Celsius to about 500 degrees Celsius at lower than the temperature that remarkable III metal nitride crystals grow occurs.
The feature of ammonia hot growing crystal III metal nitride is wurtzite structure, substantially not containing any cube of entity, and has about 2cm at about 385 nanometers to the wavelength of about 750 nanometers -1following photoabsorption coefficient.The hot growing gallium nitride crystal of ammonia can comprise crystalline substrate component, described crystalline substrate component length is greater than about 5 millimeters, there is wurtzite structure, substantially not containing other crystalline structure, other crystalline structure relative to a large amount of wurtzite structure for being less than about 0.1 volume %, impurity concentration be in Li, Na, K, Rb, Cs, Mg, Ca, F and Cl at least one be greater than 10 14cm -1, be greater than 10 15cm -1, or be greater than 10 16cm -1, be about 2cm at about 385 nanometers to the photoabsorption coefficient of wavelength of about 750 nanometers -1below.The hot growing gallium nitride crystal of ammonia can be semi-insulated, and resistivity is greater than 10 7Ω-cm.The hot growing gallium nitride crystal of ammonia can be n-type semiconductor, and carrier concentration n is 10 16cm -3to 10 20cm -3with carrier mobility η (unit is square centimeter/weber), be greater than about-0.018557n to make the denary logarithm of η 3+ 1.0671n 2-20.599n+135.49.The hot growing gallium nitride crystal of ammonia can be p-type semiconductor, and carrier concentration n is 10 16cm -3to 10 20cm -3with carrier mobility η (unit is square centimeter/weber), be greater than about-0.6546n+12.809 to make the denary logarithm of η.
By the growth of one section of right times, ammonia hot growing crystal III metal nitride can have the thickness being greater than about 1 millimeter, and is greater than length or the diameter of about 20 millimeters.In a preferred embodiment, length is greater than about 50 millimeters or be greater than about 100 millimeters.The feature of crystalline Ill-nitride thing is that crystallography radius-of-curvature is greater than 100 meters, is greater than 1000 meters or be greater than can measured value (infinitely).After growth, ammonia hot growing crystal III metal nitride can be cut into slices according to methods known in the art, polishing and chemically machinery polished to be to form one or more wafer or crystalline substrate component.In a preferred embodiment, the rootmean-square of the surfaceness of at least one wafer or crystalline substrate component for being less than about 1 nanometer, such as by atomic force microscope at least about the area of 10 microns × 10 microns is measured.
In another embodiment, polycrystalline III metal nitride is used as the raw material of the flux growth of at least one group III metal nitride single crystal, as United States Patent (USP) 7,063,741 and U.S. Patent application 2006/0037529 (being incorporated to all by reference of text herein) described in.Polycrystalline III metal nitride and at least one flux are placed in crucible and insert a stove.Stove is heated, polycrystalline III metal nitride at higher than the temperature of about 400 degrees Celsius and higher than about 1 atmospheric pressure under process in molten flux, in the process at least partially etched the and recrystallization of polycrystalline III metal nitride at least one group III-nitride crystal.Getter remaining in polycrystalline III metal nitride is progressively discharged in solution along with polycrystalline III metal nitride etches.When in the solution, getter can react and form getter metal nitride, acid amides or halogenide.Getter also can with oxygen chemical bonding.Getter can remove oxygen remaining in melting melt, to grow the group III-nitride monocrystalline having and improve purity.
Although with the complete description of upper chamber's particular, various amendment can be used, replace structure and Equivalent.Therefore, foregoing description and example illustrate the restriction can not regarded as the scope that the present invention is defined by the claims.
Following content corresponds to the original claims in parent application, and an existing part as specification sheets is incorporated to herein:
1. a composition, comprising:
Have the polycrystalline III metal nitride materials of multiple crystal grain, the feature of described multiple crystal grain is columnar structure;
The median size of one or more crystal grain in described crystal grain is that about 10 nanometers are to about 1 millimeter;
The atomic fraction of III metal in described III metal nitride is about 0.49 to about 0.55, and the described metal in described III metal nitride is at least selected from aluminium, indium or gallium; With
About 10ppm is less than as III metal oxide or as the oxygen level in the described III metal nitride materials of the replacement impurity in III metal nitride.
2. the composition described in 1, wherein said III metal comprises gallium, and described III metal nitride comprises gan, and described III metal oxide comprises Ga 2o 3.
3. the composition described in 1, the porosity that wherein said polycrystalline group III-nitride has counts about 0.1% of described metal nitride materials to about 30% with volume fraction, and apparent density is about 70% to about 99.8% of the theoretical density corresponding to described metal nitride.
4. the composition described in 1, also comprises the getter higher than about 200ppm content.
5. the composition described in 4, wherein said getter comprises metal.
6. the composition described in 4, wherein said getter comprises at least one in alkaline-earth metal, scandium, titanium, vanadium, chromium, yttrium, zirconium, niobium, rare earth metal, hafnium, tantalum and tungsten.
7. the composition described in 4, the amount that wherein said getter exists is greater than about 0.1%.
8. the composition described in 7, wherein said getter comprises metal.
9. the composition described in 7, wherein said getter comprises at least one of alkaline-earth metal, scandium, titanium, vanadium, chromium, yttrium, zirconium, niobium, rare earth metal, hafnium, tantalum and tungsten.
10. the composition described in 2, wherein with Ga 2o 3or with the content replacing the described oxygen that impurity exists in gan for being less than about 3ppm.
Composition described in 11. 2, wherein with Ga 2o 3or with the content replacing the described oxygen that impurity exists in gan for being less than about 1ppm.
Composition described in 12. 1, the feature of wherein said multiple crystal grain is that the mean number of crystal grain is about 100/ cubic centimetre to about 10,000/ cubic centimetre.
Composition described in 13. 1, the described porosity of wherein said metal nitride counts about 0.1% to about 10% with volume fraction.
Composition described in 14. 1, the described porosity of wherein said metal nitride counts about 10% to about 30% with volume fraction.
Composition described in 15. 1, also comprises the average crystal grain diameter being greater than about 1 millimeter.
Composition described in 16. 1, comprises the average crystal grain diameter of about 1 millimeter to about 10 microns.
Composition described in 17. 1, also comprises the average crystal grain diameter being greater than about 1.0 microns.
Composition described in 18. 1, the apparent density of wherein said polycrystalline metal nitride is about 85% of described theoretical value to about 95%.
Composition described in 19. 1, the atomic fraction of metal described in wherein said metal nitride is about 0.50 to about 0.51.
Composition described in 20. 1, also comprises the one or more of one or more of doping agents that can produce in N-shaped material, p-type material or semi insulating material.
Composition described in 21. 20, also comprises and is greater than about 10 21the concentration of dopant of atom/cubic centimetre.
Composition described in 22. 21, wherein said concentration of dopant is about 10 21atom/cubic centimetre is to about 10 16atom/cubic centimetre.
Composition described in 23. 1, wherein said polycrystalline metal nitride has the intercrystalline flexural strength being greater than about 20 MPas.
Composition described in 24. 1, wherein said polycrystalline metal nitride has from being greater than the intercrystalline flexural strength of about 20 MPas to about 90 MPas.
Composition described in 25. 1, wherein said polycrystalline metal nitride has the intercrystalline flexural strength being greater than about 90 MPas.
26. 1 kinds of methods, comprising:
In at least one crucible, provide III metal, described III metal comprises at least one metal be at least selected from aluminium, gallium and indium;
Thering is provided relative to described III metal is the getter of at least 100ppm content, and described getter is at least selected from alkaline-earth metal, scandium, titanium, vanadium, chromium, yttrium, zirconium, niobium, rare earth metal, hafnium, tantalum and tungsten;
Described III metal in described crucible and described getter are provided in chamber;
Transfer nitrogenous material is in described chamber;
Described chamber is heated to and determines temperature;
Described chamber is pressurized to and determines pressure;
In the cavity by nitrogenous material described in described III metal treatment; With
At least in containing the described crucible of described III metal, form polycrystalline III metal nitride.
Method described in 27. 26, wherein said getter comprises the one or more of materials be selected from calcium, strontium, barium, zirconium, hafnium and tantalum.
Method described in 28. 26, is wherein provided to described getter in described crucible together with described III metal.
Method described in 29. 26, wherein said getter is greater than 300ppm relative to the content of described III metal.
Method described in 30. 29, wherein said getter is greater than about 0.1% relative to the content of described III metal.
Method described in 31. 30, wherein said getter is greater than about 1% relative to the content of described III metal.
Method described in 32. 26, also comprises and provides doping agent or dopant precursor.
Method described in 33. 26, also comprises and hydrogen halide is transferred to described chamber to mix with described nitrogenous material.
Method described in 34. 26, also comprise and described III metal is contacted with one or more of wetting agent, wherein said wetting agent comprises bismuth, germanium, tin, lead, antimony, tellurium, polonium or their combination.
Method described in 35. 26, also comprises:
Cool described chamber;
Described polycrystalline group III-nitride is shifted out from described chamber;
Described polycrystalline group III-nitride and ammonia are provided in autoclave or sealed cabin together with mineralizer; With
In supercritical ammine higher than about 400 degrees Celsius temperature and higher than the pressure of 0.2GPa under process described polycrystalline group III-nitride.
Method described in 36. 35, wherein said mineralizer comprises at least one in alkali and alkaline earth metal ions.
Method described in 37. 36, also comprises and provides additional getter, and described additional getter comprises at least one in Be, Mg, Ca, Sr, Ba, Sc, Y, rare earth metal, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo or W.
Method described in 38. 35, wherein said mineralizer comprises at least one in muriate and fluorochemical.
Method described in 39. 38, also comprises the additional getter provided containing at least one in Sc, Cr, Zr, Nb, Hf, Ta or W.
Method described in 40. 26, also comprises:
Cool described chamber;
Described polycrystalline group III-nitride is shifted out from described chamber;
Described polycrystalline group III-nitride is provided in stove together with flux; With
In molten flux higher than about 400 degrees Celsius temperature and process described polycrystalline group III-nitride under being greater than 1 atmospheric pressure.
41. 1 kinds of formation, containing the method for the substrate of III metal nitride, comprising:
There is provided III metal as raw material, described III metal comprises at least one metal be at least selected from aluminium, gallium and indium;
Thering is provided relative to described III raw metal content is the getter of at least 100ppm;
Described III raw metal and described getter are provided in chamber;
Transfer nitrogenous material is in described chamber;
Described chamber is heated to and determines temperature;
Described chamber is pressurized to and determines pressure;
In the cavity by nitrogenous material described in the process of described III raw metal;
Forming crystal III metal nitride, it is characterized by wurtzite structure, substantially not containing any cubic structure composition, is about 2cm at about 385 nanometers to the photoabsorption coefficient at the wavelength place of about 750 nanometers -1below.
42. 1 kinds of nitrogen gallium crystal, comprising:
Crystalline substrate component, its length is greater than about 5 millimeters;
Basic wurtzite structure, is characterized in that substantially not containing other crystalline structure, other crystalline structure described relative to the volume of described basic wurtzite structure for being less than about 1 volume %;
Be selected from the impurity concentration of at least one in Li, Na, K, Rb, Cs, Mg, Ca, F and Cl and be greater than 10 15cm -1; With
Be about 2cm at about 385 nanometers to the photoabsorption coefficient at wavelength place of about 750 nanometers -1below.
Gallium nitride described in 43. 42, other structures wherein said are for being less than about 0.5 volume %.
Gallium nitride described in 44. 42, other structures wherein said are for being less than about 0.1 volume %.
Gallium nitride described in 45. 42, wherein said crystalline substrate component is n-type semiconductor, is characterised in that carrier concentration n is 10 16cm -3to 10 20cm -3, and the carrier mobility η in units of square centimeter/weber makes the denary logarithm of η be greater than about-0.018557n 3+ 1.0671n 2-20.599n+135.49.
Gallium nitride described in 46. 42, wherein said crystalline substrate component is p-type semiconductor, is characterised in that carrier concentration n is 10 16cm -3to 10 20cm -3, and the carrier mobility η in units of square centimeter/weber makes the denary logarithm of η be greater than about-0.6546n+12.809.
Gallium nitride described in 47. 42, wherein said crystalline substrate component is semi-insulated, and resistivity is greater than 10 7Ω-cm.
Gallium nitride described in 48. 42, is characterised in that the impurity concentration of at least one in Li, Na, K, Rb and Cs is greater than 10 15cm -1, and Be, Mg, Ca, Sr, Ba, Sc, Y, rare earth metal, at least one in Ti, Zr, Hf, V, Nb, Ta, Cr, Mo or W impurity concentration be greater than 10 14cm -1.
Gallium nitride described in 49. 42, is characterized in that in F and Cl, the impurity concentration of at least one is greater than 10 15cm -1, and in Sc, Cr, Zr, Nb, Hf, Ta or W, the impurity concentration of at least one is greater than 10 14cm -1.
Crystal described in 50. 42, other crystalline structure wherein said comprise cubic structure.
Crystalline structure described in 51. 42, wherein said crystalline substrate component comprises gan.
Crystalline structure described in 52. 42, wherein said crystalline substrate component comprises gallium material and nitrogen material.
Crystalline structure described in 53. 42, wherein said substrate member has the thickness being greater than about 1 millimeter.
Crystalline structure described in 54. 42, wherein said length is greater than about 20 millimeters.
Crystalline structure described in 55. 42, wherein said length is greater than about 50 millimeters.
Crystalline structure described in 56. 42, wherein said length is greater than about 100 millimeters.
Crystalline structure described in 57. 42, the feature of wherein said crystalline substrate component is that crystallography radius-of-curvature is greater than 100 meters.
Crystalline structure described in 58. 42, the feature of wherein said crystalline substrate component is that crystallography radius-of-curvature is greater than 1000 meters.
Crystalline structure described in 59. 42, the feature of wherein said crystalline substrate component is infinitely-great crystallography radius-of-curvature.
Crystalline structure described in 60. 42, wherein said crystalline substrate component has the root mean square surfaceness of below 1 nanometer.

Claims (19)

1., containing a gallium crystal, comprising:
Crystalline substrate component, its length is greater than about 5 millimeters;
Basic wurtzite structure, is characterized in that substantially not containing other crystalline structure, other structure described relative to the volume of described basic wurtzite structure for being less than about 1 volume %;
Be selected from the impurity concentration of at least one in Li, Na, K, Rb, Cs, Ca, F and Cl and be greater than about 10 15cm -3; With
Be about 2cm at about 385 nanometers to the photoabsorption coefficient of wavelength of about 750 nanometers -1below.
2. according to claim 1 containing gallium crystal, other structure wherein said is for being less than about 0.5 volume %.
3. according to claim 1 containing gallium crystal, other structure wherein said is for being less than about 0.1 volume %.
4. according to claim 1 containing gallium crystal, wherein said crystalline substrate component is n-type semiconductor, it is characterized in that carrier concentration n is about 10 16cm -3to 10 20cm -3, and the carrier mobility η in units of square centimeter/weber makes the denary logarithm of η be greater than about-0.018557 (log 10n) 3+ 1.0671 (log 10n) 2-20.599 (log 10n)+135.49.
5. according to claim 1 containing gallium crystal, wherein said crystalline substrate component is p-type semiconductor, is characterised in that carrier concentration n is about 10 16cm -3to 10 20cm -3, and the carrier mobility η in units of square centimeter/weber makes the denary logarithm of η be greater than about-0.6546 (log 10n)+12.809.
6. according to claim 1 containing gallium crystal, wherein said crystalline substrate component is semi-insulated, and resistivity is greater than 10 7Ω-cm.
7. according to claim 1 containing gallium crystal, it is characterized in that the impurity concentration of at least one in Li, Na, K, Rb and Cs is greater than 10 15cm -1, and Be, Mg, Ca, Sr, Ba, Sc, Y, rare earth metal, at least one in Ti, Zr, Hf, V, Nb, Ta, Cr, Mo or W impurity concentration be greater than 10 14cm -1.
8. according to claim 1 containing gallium crystal, it is characterized in that in F and Cl, the impurity concentration of at least one is greater than 10 15cm -1, and in Sc, Cr, Zr, Nb, Hf, Ta or W, the impurity concentration of at least one is greater than 10 14cm -1.
9. according to claim 1 containing gallium crystal, other crystalline structure wherein said comprise cubic structure.
10. according to claim 1 containing gallium crystal, wherein said crystalline substrate component comprises gan.
11. is according to claim 1 containing gallium crystal, and wherein said crystalline substrate component comprises gallium material and nitrogen material.
12. is according to claim 1 containing gallium crystal, and wherein said substrate member has the thickness being greater than about 1 millimeter.
13. is according to claim 1 containing gallium crystal, and wherein said length is greater than about 20 millimeters.
14. is according to claim 1 containing gallium crystal, and wherein said length is greater than about 50 millimeters.
15. is according to claim 1 containing gallium crystal, and wherein said length is greater than about 100 millimeters.
16. is according to claim 1 containing gallium crystal, and the feature of wherein said crystalline substrate component is that crystallography radius-of-curvature is greater than 100 meters.
17. is according to claim 1 containing gallium crystal, and the feature of wherein said crystalline substrate component is that crystallography radius-of-curvature is greater than 1000 meters.
18. is according to claim 1 containing gallium crystal, also comprises the impurity concentration of at least one in Li, Na, K, Rb, Cs, Ca, F and Cl and be greater than about 10 16cm -3.
19. is according to claim 1 containing gallium crystal, and wherein said crystalline substrate component has the rms surface roughness of below 1 nanometer.
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